Process for the preparation of unsaturated carbonyl compounds

ABSTRACT

A process for the preparation of unsaturated carbonyl compounds which comprises carrying out the catalytic vapor phase oxidation of an olefin selected from the group consisting of propylene and isobutylene in the presence of a catalytic oxide in which the atomic ratio among the constituent catalytic elements, Co:Fe:Bi: W:Mo:Si:Tl:Z ranges 2.0-20.0 : 0.1-10.0 : 0.1-10.0 : 0.5-10.0 : 2.0-11.5 : 0.5-15.0 : 0.005-3.0 : 0-3.0, with the proviso that W plus Mo equals 12.0, and Z stands for a metal selected from the group consisting of alakali metals and alkaline earth metals.

ll'nited States Patent [191 Ueshima et al.

[ Dec. 17, 1974 22 Filed:

[ PROCESS FOR THE PREPARATION OF UNSATURATED CARBONYL COMPOUNDS [75] Inventors: Michio Ueshima, Nishinomiya; Isao Yanagisawa, Ikeda; Masahiro Takata, Toyonaka; Michikazu Ninomiya, Kobe, all of Japan [73] Assignee: Nippon Shokubai Kagaku Kogyo Co., Ltd., Osaka, Japan June 6, 1972 [21] App]. No.: 260,222

[ 30] Foreign Application Priority Data June 9, 1971 Japan 46-40128 [52] U.S. Cl. 260/604 R, 252/469, 260/533 R [51] Int. Cl. C07c 45/04 [58] Field Of Search 260/604 R [56] I References Cited UNITED STATES PATENTS 2/1953 Connolly et a1 260/604 R 3,177,257 4/1965 Detling et a]. 260/604 R 3,522,299 7/1970 Takevaka et a] 260/604 R X 3,679,603 7/1972 Garnish et al 260/604 R X Primary Examiner-Leon Zitver Assistant Examiner-D. B. Springer Attorney, Agent, or Firm-Sherman & Shalloway [5 7] ABSTRACT A process for the preparation of unsaturated carbonyl compounds which comprises carrying out the catalytic vapor phase'oxidation of an olefin selected from the group consisting of propylene and isobutylene in the 10 Claims, No Drawings PROCESS FOR THE PREPARATION OF UNSATURATEDCARBONYL' COMPOUNDS As the catalyst conventionally employed in the preparation of acrolein or methacrolein by the catalytic vapor phase oxidation of propylene or isobutylene, respectively, the catalytic oxide composed of oxygen, molybdenum, tellurium and either cadmium or zinc is recommended, for example, by the prior art disclosed in Japanese Official Patent Gazette, Publication No. 10605/68. Also, Japanese Patent, Publication No.

'6245/69 teaches the use of the catalytic oxide composed of nickel, cobalt, iron, bismuth, molybdenum, phosphorus and oxygen and which is developed by adding nickel, cobalt and phosphorus to the catalytic oxide composed of iron, bismuth, molybdenum and oxygen. However, the per-pass yield of the unsaturated carbonyl compounds obtained through the action of these known catalysts are not quite fully satisfactory when considered from the standpoint of commercial productron.

It is therefore an object of this invention to provide by the discovery of a new catalyst a process for the preparation of the unsaturatedcarbonyl compounds, which can be favorably employed in commercial,pro-' duction.

We have discovered that the above object of the invention can be accomplished by the use of a catalytic oxide which comprises cobalt, iron, bismuth, tungsten, molybdenum, silicon, thallium and oxygen, or a catalytic oxide. comprising cobalt, iron, bismuth, tungsten, molybdenum, silicon, thallium, alkali metals or alkaline earth metals and oxygen, since in the presence of such hydroxides are also usually useable conveniently. On

the other hand, as the compounds of alkali metals, the

aqueous solutions of respectively cobalt nitrate, ferric nitrate, bismuth nitrate and thallium nitrate,'as well as the aqueous solution of a hydroxide or nitrate of an alkali metal or alkaline earth metal and subsequently coloidal silica as the silicon source, then adding a carrier, if necessary, followed by concentrating the system by evaporation, moulding the resulting clay-like substance and calcining the same at temperatures between i 350 600 C.,-in'a stream of air. Obviously, the starting materials of the catalyst are not limitedto the foregoing ammonium salt, nitrates, hydroxides and carbonates, but various other compounds are equally useful so far as they can form the catalytic oxide upon calcination.

a catalyst acrolein or methacrolein is obtained from propylene or isobutylene, respectively, with a very high per-pass yield. I

The catalyst or catalytic oxide of the invention is characterized in that the catalytic elements constituting the same are present in the atomic ratios: Co:Fe:Bi:W- :Mo:Si:Tl:Z =2.0-20.0 0.l-l0.0 0.l-10.0 0.5-10.0 2.0-1 [.5 0.5-15.0 0.005-30 03.0 (provided that W Mo 12.0, and Z stands for alkali metal and/or alkeline earth metal). Presumably, the oxygen is present in the catalyst in the form of complex metal oxide or metallic acid salt. Consequently, the oxygen content of the catalyst varies depending on the atomic ratios of the catalytic elements.

The oxides of the respective metals can be used as the starting material of the catalyst in the present in- As the carrier, for example, silica gel, alumina, silicon carbide, diatomaceous earth, titanium dioxide and Celite, etc. may be employed. Particularly preferred carriers are silica gel, titanium dioxide and Celite.

The catalytic vapor phase oxidation in accordance with the invention is performed byintroduc'ing a gaseous mixture composed of l 10 vol. of propylene .or isobutylene, 5 l8 vol. of molecular oxygen, 10 vol. 7e of steam and 20 vol. of an inert gas, over the catalyst prepared at above, at temperatures ranging from 250 450C. and pressures ranging from the normal pressure to 10 atmospheres. A suitable contact timeranges from 0.5 to 10.0 seconds. The reaction can be carried out either with a fixed bed or fluidized bed.,

By operating in the foregoing manner, results such as 92.5 98 mol conversion of propylene or isobutylene, 92 mol selectivity for acrolein and 78 84 mol selectivity for methacrolein can be obtained.

These achievements are markedly superior to those of the prior art.

Although the subject invention is not to be restricted by any theory, the excellent results of the invention process arejpresumably due to the appropriate adjustment of catalytic ability accomplished by the concurrent presence, in the catalytic oxide of the invention, of

molybdates and tungstates of cobalt, iron, and bismuth,

in addition to the oxides; as well as thepresence of.

' heteropolyacid compounds containing silicon, thalvention. However, in the case of molybdenum and I tungsten, the acid salts such as ammonium molybdate and ammonium tungstate are conveniently used. Further, in the case of the other metals, the use of the water-soluble salts such as nitrates and carbonates and lium, alkali metals and alkaline earth metals. Especially, the effects due to the presence of thallium and silicon are substantiated by the facts that the selectivities are markedly improved by the presenceof thallium and that the conversion is improved by the presence of silicon, while retaining the high level of selectivities, as demonstrated in the hereinafter given Example 1 and Controls 1 and 2.

The terms, conversion, selectivity, and perpass yield, as used herein, are defined as follows:

Conversion Number of mols of olefin CONTROL 2 reacted/Number of mols of olefin supplied X 100 Selectivity Number of mols of unsaturated carbonyl compound formed/Number of mols of olefin reacted X 100 per-pass yield Number of mols of unsaturated Example 1 was repeated except that the use of thallium nitrate was omitted. The composition of the catalyst in terms of atomic ratio was as follows:

C F81 1 2 ms.

carbonyl compound formed/Number of mols of olefin This catalyst was used and the reaction was carried supplied X 100 out as in Example 1, with the results shown in Table l.

Table l Composition of catalyst Reaction Propylene Selectivity Per-pass ield (atomic ratio) temperature conversion (mol (mol Co Fe Bi W Mo Si Tl (C) (mol Acro- Acrylic Acro- Acrylic lein acid lein acid Example l 1 l 2 10 1.35 0.05 300 97.5 91.5 6.0 89.2 5.9 Control 1 l l 2 10 0.05 300 84.0 93.0 2.5 78.1 2.1 Control The invention will be more fully illustrated by refer- EXAMPLE 2 ence to the following examples and control experimerits, it being understood that the scope of this invention is by no means restricted thereby.

The reaction was carried out by operating as in Example 1 using the catalyst used therein, except that the reaction temperature used was 330C. and the contact EXAMPLE 1 time was 1 second.

Seventy (70.0) g of cobalt nitrate was dissolved in 20 The results are as follows: ml of distilled water, also 24.3 g of ferric nitrate was dissolved in 20 of distilled water, and 29.2 g of bismuth Conversion of p py 96.0 mol nitrate, 'was dissolved in 30 ml of distilled water which Selectivity f acrolein 9L0 mo] was made acidic with 6 ml of cone. nitric acid. Sepa- Selectivity for acrylic acid 5.8 mol,%

rately, into 300 ml of water, 106.2 g of ammonium molybdate and 32.4 g of ammonium p-tungstate were dissolved with heating and stirring. The foregoing three EXAMPLE 3 aqueous solutions of nitrates were added dropwise into the latter aqueous solution of ammonium salts, and further an aqueous solution formed by dissolving 0.801 g of thallium nitrate in 10 ml of distilled water and 24.4

g of 20% silica sol were added thereto. The so formed suspension was heated with stirring to cause the evaporation of the liquid component. The resulting solid was moulded and calcined at 450C. for 6 hours in a stream The reaction was carried out as in Example 1 using the catalyst used therein, a reaction temperature of 300C, a contact time of 1.4 seconds, and asthe reactant gas a gas mixture composed of 7 vol. of propylene, 63 vol. of air and 30 vol. of steam. The results obtained are as follows:

of air to form the catalyst. The composition of the cata- Conversion f propyhne 975 mol% lytic elements in terms of atomic ratio was as indicated Selectivity for acrolein 89.0 mol below: Selectivity for acrylic acid 7.1 mol i 1 4 i B 1 2 10 1.35 T 0.05 I EXAMPLES 4 8 Sixty ml of the thus obtained catalyst was packed in a stainless steel U-shaped tube of 25 mm diameter. The Catalysts of the composmons Show m Table 2 were tube was immersed in a molten nitrate bath heated at prepared by as in Example In the casiof 300C, and a gaseous mixture composed of 5 vol. f Example 6, 20 weight 70, based on the catalyst, of silica propylene, vol. of air and 40 vol. of steam was 55 gel was used as a earner however' introduced into the tube and reacted with a contact These catalysfs used and y p g 35 time of 1.4 seconds. The results obtained are shown in ample 1 the oxldatlon of P py was earned out at T bl 1 the reaction temperatures indicated in Table 2, with the results shown therein. CONTROL 1 Example 1 was repeated except that the addition of EXAMPLE 14 silica sol was omitted. The composition of the resulting Catalysts having the COmPQSIIiOIIS Show" In a e 2 catalyst in terms of atomic ratio was indicated below: were P p y Operating as in mpl 1 x ep ha as the starting material of the catalyst the hydroxides or C0 Fe. Bi, W, Mo T1 nitrates of alkali metals and/or alkaline earth metals This catalyst was used and the reaction was carried were used in addition to the compounds used in Examout' as in Example 1, with the results also shown in ple l. ln'the case of Example 9. 30 weight based on Table l. the catalyst, of titanium dioxide was used as a carrier.

These catalysts were used and by operating as in Example 1 the oxidation of propylene was carried out at the reaction temperatures indicated in Table 2, with the results shown therein.

3. The process of claim 1 in which methacro prepared by using isobutylene.

4. The process of claim 1 in which the oxidation is performed on agaseous mixture of l to volume per- Table 2 Composition of catalyst (atomic ratio) Reaction Propylene Selectivity Per-pass yield I Alkali temperaconver- (mol (mol Example Alkali earth ture 'sion Acro- Acrylic Acro- Acrylic No. Co Fe B1 W Mo Sl Tl metal metal (C.) (mol "(21) lein acid lein acid 4 4 l 1 2 10 1.35 0.08 300 96.5 92.1 5.0 88.9 4.8 5 4 l l 3 9 2.0 0.10 4 295 97.0 91.5 5.7 88.8 5.5 6 5 g l 2 1 ll 1.1 0.05 310 98.2. 87.0 7.5 85.4 7.4 7 4 0.5 l l 11 1.5 0.05 290 97.5 90.8 6.8 88.5 6.6 8 4 2.0 1 2 10 1.0 0.05 N 320 98.0 88.0 7.1 86.2 7.0

a 9 4 l l 2 10 1.35 0.03 0.]( 305 97.5 86.5 8.0 84.3 7.8 '10 4 l l 2 l0 1.35 0.03 0.03 q 315 97.0 88.0 6.2 85.4 6.0 7 1-1 4 1 2 10 1.35 0.03v 0 0 300 97.2 86.8 7.5 84.4 7.3

8 l2 4 l l 2 10 1.35 0.03 0.05 305 96.5 87.0 6.8 84.0 6.6

Na Mg 13 4 l l 2 10 1.35 0.03 0.23 O(.:03 300 98.2 85.9 8.2 84.4 811 EXAMPLE l5 18 cent of propylene or isobutylene, 5 to 18 volume per- Catalysts of'various compositions as shown in Table cent of g g zfi i 10 to 60 percent of 3 were prepared as in Example 1 and Examples l4. j I to f qq ii' g an Sixty ml of each of these catalysts was packed in a d v e i f s O f l 3 g'n stainless steel U-shaped tube of 25 mm diameter, and 2 2 Con ac i mm O secton the tube was immersed in a molten nitrate bath heated b 1 process g fiPg 0 ,unsa.ura e $3:- at 310C.. following which a gaseous mixture com- {Compoun 2 l i i ii t g posed of 5 vol. of isobutylene. 55 vol. of air. and F 3 "1 25 133 25f zgss vol. 7r of steam was introduced and reacted with a 35 s g gz g i l iyg; and in i contact time of 1.8 seconds. The results obtained are presence of a Catalytic Oxide in which the atomic ratio shown in Table 3. 1

Table 3 Composition of catalyst (atomic ratio) lsobutylene Methacrolein Methacrolein Example conversion selectivit per-pass yield No. Co Fe '81 W -Mo Si T1 2 (mol%) (mol (mol%) 15 4 l 1 2 10 1.35 0.3 93.0 81.5 75.8 16 6 l l 2 10 1.35 1.0 I?- 92.5 84.0 77.6

. a p 17 4 l l 2 10 1.35 0.2 ($1 94.0 79.8 75.0

' a 18 4 l l 2 10 1.35 0.2 0.1 95.0 .78.7 74.8

0 9 i We claim: 5 among the constituent catalytic elements, Co:Fe:Bl:W- 1. A process for the preparation-of unsaturated car- :Mo:Si:Tl ranges 2.0-20.0 0.1-10.0 0.1-10.0 bonyl compounds which comprises carrying out the O.5-10.0 2.0-11.5 0.515.0 0005-30, with the catalytic vapor phase oxidation of an olefin selected proviso that W plus Mo equals 12.0, at temperatures from the group consisting of propylene and isobutylranging from 250 to 450C. and pressures ranging ene, in the presence of molecular oxygen, and in the from normal pressure to 10 atmospheres. presence ofa catalytic oxide in which the atomic ratio 7. The process of claim 6 in which acrolein is preamong the constituent catalytic elements, CoiFezBizW- pared by using propylene. :Mo:Si:Tl:Z ranges 2.0-20.0 0.1-10.0 0.1-10.0 8. The process of claim 6 in which methacrolein is 0.5-l0.0 2.0-11.5 10.5-15.0 0.0053.0 0 3.0, prepared by using isobutylene. with the proviso that W plus Mo equals 12.0, and Z 9. The process of claim 6 in which the oxidation is stands for a metal selected from the group consisting of Perf med On a gaseous'mlxture 0f 1 to 10 volume perthe alkali metals and alkaline earth metals. at temperacent of propylene or isobutylene, 5 to 18 volume pertures ranging from 250 to 450C. and pressures ra-ngcent of molecula? y I0 60 l Percent Of ing from normal pressure to 10 atmospheres. steam, and 20 to volume percent of an mertgas.

2. The process of claim 1 in which acrolein is prepared by using propylene.

10. The process of claim 6 in which the catalytic oxidation contact time is from 0.5 to 10.0 seconds.

lein is I 

1. A PROCESS FOR THE PREPARATION OF UNSATURATED CARBONYL COMPOUNDS WHICH COMPRISES CARRYING OUT THE CATALYTIC VAPOR PHASE OXIDATION OF AN OLEFIN SELECTED FROM THE GROUP CONSISTING OF PROPYLENE AND ISOBUTYLENE, IN THE PRESENCE OF MOLECULAR OXYGEN, AND IN THE PRESENCE OF A CATALYTIC OXIDE IN WHICH THE ATOMIC RATIO AMONG THE CONSTITUENT CATALYTIC ELEMENTS, CO:FE:BI:W:MO:SI:TL:Z RANGES 2.0-20.0 : 0.1-10.0 : 0.1-10.0 : 0.5-10.0 : 2.0-11.5 : 0.5-15.0 : 0.005-3.0 : 0 - 3.0, WITH THE PROVISO THAT W PLUS MO EQUAL 12.0, AND Z STANDS FOR A METAL SELECTED FROM THE GROUP CONSISTING OF THE ALKALI METALS AND ALKALINE EARTH METALS, AT TEMPERATURE RNGING FROM 250* TO 450*C. AND PRESSURE RANGING FROM NORMAL PRESSURE TO 10 ATMOSPHERES.
 2. The process of claim 1 in which acrolein is prepared by using propylene.
 3. The process of claim 1 in which methacrolein is prepared by using isobutylene.
 4. The process of claim 1 in which the oxidation is performed on a gaseous mixture of 1 to 10 volume percent of propylene or isobutylene, 5 to 18 volume percent of molecular oxygen, 10 to 60 volume percent of steam, and 20 to 70 volume percent of an inert gas.
 5. The process of claim 1 in which the catalytic oxidation contact time is from 0.5 to 10.0 seconds.
 6. A process for the preparation of unsaturated carbonyl compounds which comprises carrying out the catalytic vapor phase oxidation of an olefin selected from the group consisting of propylene and isobutylene, in the presence of molecular oxygen and in the presence of a catalytic oxide in which the atomic ratio among the constituent catalytic elements, Co:Fe:Bi:W:Mo:Si: Tl ranges 2.0-20.0 : 0.1-10.0 : 0.1-10.0 : 0.5-10.0 : 2.0-11.5 : 0.5-15.0 : 0.005-3.0, with the proviso that W plus Mo equals 12.0, at temperatures ranging from 250* to 450*C. and pressures ranging from normal pressure to 10 atmospheres.
 7. The process of claim 6 in which acrolein is prepared by using propylene.
 8. The process of claim 6 in which methacrolein is prepared by using isobutylene.
 9. The process of claim 6 in which the oxidation is performed on a gaseous mixture of 1 to 10 volume percent of propylene or isobutylene, 5 to 18 volume percent of molecular oxygen, 10 to 60 volume percent of steam, and 20 to 70 volume percent of an inert gas.
 10. The process of claim 6 in which the catalytic oxidation contact time is from 0.5 to 10.0 seconds. 